Dialkyl bisphenoxy acetate plasticized polyvinyl chloride compositions



Patented July 15, 1952 nianxyriprsrimnoxy AGETATE, PLASTL cnronnm oomrosr- CIZED 'POLYVINYL TIONS Joachim Dazzi, Dayton, Ohio, assignor to Mon- '1 santo Chemical Company, St Louis ll lo a eorporation of Delaware 1; l V "No Drawing". Application-February 23; 1950, r

a ;Srial No.- 145,889;.' y

This invention relates to newsplasticcompositionScbmpriSing lvinylchloride and'an ester of l bisphenoxyacetic acid which. may be represented by the followmg formula: 1 .1

-wiiriii R is an 'alkylradial. manages than 11 carbon atoms.

Compositions based onf'polyvinyl chloride .are 1 among themost-wldely used plastic materials currently available. Polyvinyl chloride,- per5se howevertis' a-hard, horny, brittle. material which 1 has little utility.. 7 This imaterial ris modified by the incorporation of a plasticizer to provide; a large range of compositions-of varying physical ;;'Viny1;i chloride may be copolymerized with other monomers, as for example a small amount or vinyl acetate to' also, materially improve the general physical properties of the-vinyl chloride resna -Copolymers of this nature, wherein the vinylchloride is the major resin constituent, may also lee-further modified by-the incorporation of ajplasticizerg Polymer materials which can. be plasticizcd by. the dialkyl bisphenoxyacetates 'disclosed: herein are polyvinyl chloride and copolymers of vinyl chloride wherein the-vinyl chloride comprises atleast about-80 per cent'by weight of the-resin composition and up to aboutzoper cent-of a copolymerizable:monomer q 1 --lvlany plasticizers havebeen recommended and are used for formulation with vinyl. chloride resins. However, for various reasons none of the plasticizers available provides the. optimum conditions .for all physical properties. Currently the most widelyused .general polyvinyl chloride plasticizers are tricresyl phosphate and d1 2- ethylhexyl phthalate.

Recently cresylic acidand phthalic anhydride were in'short supply and plasticizers became'the bottleneck of the plastics industry This condition has t now been alleviated but it points out the necessity of having a large range of suitable plasticizers available from varying sources; This wouldfbe desirable even if thanew plasticizers might be somewhat interior} in e,rtain physical properties to the currently favoredplasticizers.

. It is oflcourse understood that the ultimate end use of the vinyl chloride plastic will determine the essential physical properties required. Thus; for 'many specialty applications certain specific properties may be ignored, if unimportant for the intendedapplication. t V

The object or this invention is to provide plasticized vinyl chloride compositions wherein the plasticizeris economical, compatible with the vinyl chloride composition over a wide range of invention:

f oftem 'I'he'plasticizeras erali be employed from about 5.1!}: itoabout; 45 per cent by weight of the final-composition and preferably from, about 20 to about 45. .per cent.

proportions, and is effective 7 v v rature variations other objects willbe apparent from the following disclosure.

' It has m res; found that .coinpbsjitionsof polyvinyl chloride with Ltd 10 carbonatom saturated alkyl monohydric alcohol esters or bisfphenoxyacetic acid provide resins which have chemical and physical characteristics which are comparable to the best general plasticizers currently, employed. The ester alkyl radicals can be mixed or identical. The esters can be 0,05;

o,p-; m,m'-; and p,p'-. However, the esters of p,p'- bisphenoxyacetic acid are preferred for their ease of preparation and the lower volatility which they impart to the polyvinylchloridegresin co s t above identifiedmay ingen- The polyvinyl chloride composition also nearly always has a stabilizer to protect the resin from thermal decomposition and degradation of color. In addition, fillers, coloring materials, and mold lubricants may be added as is well-known to I those familiar with the art. I

Mixed plasticizers may also be employed from among the above disclosed estersandsuitable prior art plasticizers. i

The following examples are-illustrative-of this w mb l A. An alk'aline's'olutionwas'prepared by dissolvin'g 88 g. -(2.'2'm oles)- ofsodium' hydroxide in 250 ml. of' water to which 204.6 g: (1.1 moles) of '4,4'-dihydroxybiphenylwas charged and dissolved-therein. Then about mLpfeth'a-nol was-added thereto. t

B; A-second solution was preparedby dissdlvingfflfiig. (1.45moles) of sodium 'carbon a'te in=about 450 ml. of water and then dissolving therein 274 g. (2.9 moles) of monochloroacetic acid.

SolutionA wasslowly added to solution B over a period of about 2 hours while maintaining mild agitation. "It was necessary to maintain the sodium p-,p"-biphenate at about 40 to 50 C. to prevent crystallization from taking place in the concentrated solution. Mild agitationwas continued overnight at room temperature.= The reaction, mixture was then poured into} liters-of water and made strongly acid'by slowly adding hydrochloric acid while rapidly stirring the solution. The p,p-bisphenoxyacetic acid was precipitated and recovered by filtration, resuspended in 3 liters of wash water and stirred-for? hours, then again filtered. The p,p'- bisphenoxyacetic acid was thensuspen'ded in 1 liter ofhot ethanol; stirred to dissolvean'y unreacted 4,4"-dihydroxy- =biphenyl present in the product, and'again illover a wide range 'V was found to be slow. When the esterification V anf 'radical containing. less a 3 eos jti i lo' lf' i ,1 hfl in't es r: .iw i

eye the white was then dried.

Example 2 piY-jbsis i etamaic 45 g. (0.15 mole) '23 g. (0.60 mole) 2-ethylhi'ano. 150 ml. benzene.

1 g. toluene sulionic acid.

The mixture of the above reactants was heated under reflux and the water formed during the esterification was collected in' aIDean and Stark-L':..., t .o. i

than ll carbon atoms.

distilling receiver. Esterification was further a'cicelerated by the addition of 5 ml. of concentrated. I

sulfuric acid, when themate of water formation fwa'sfcoinplete' as measured by fthe cessation of water form fjon; the reaction mixture was cooled and a 1 small amount; of insoluble material was utfthen the liquid-was diluted with ethyl l i. b ast g I twice; with" water. The solvents were .icati Th-ei-z r ard'polyvinyl chloride composition inan amount sufficien't 'to provide 40 per cent a plasticizer on the 'ba sb'f the'tot'al composition'and evaluated P in t fi'etable Tirol Percent Volatility 24 hrs. atl105h Percent WaterAbsorption 24 hrs Percent Water Leaching Loss 24hrs Cle'shendBerg method. TCP=trieresyl phosphate. DOP=di-2 -ethylhexyl phthalate.

The plasticizer oi this invention did not exhibit any fuming during "milling with the polyvinyl h p i- -rwa c ti le herew th. a the tra spa 'encYbf-t e o d d. he wa he H Qther suitable. esters of bisphenoxyacetic acid which -may -be compounded withvinyl chloride resins are for example dimethyl;p,p'- bis phen oxyacetate; diethyl-p,p'-bisphenpxyacetat6;; di-

; but l-p 12':b sphenoxy etatez;--- ex l-nn-b nhendx a eta w n oth r h o ou s poundsg whereinthealkyl group contains less than--11 carbonatoms. 1 1 I v I claim: 1 A plasticized vinyl chloride resin which comgprises agpolygner of at least about per cent of 7 vinyl chloride andup to about 20 per ,cent oia .copolymerizable monomer, containing intimately dispersed therein a l-ester, of bisphenoxyacetic acid havingqtheformula pom-ope than. l 1 carbon atoms:

2.; The .plasti'ci'zedwinyl chloride t comprise itsvinyl chloride and up to about 20 per cent of a wherein ,R is an alkyl radical containing less 4 The plasticized vinyl chloride resin compositionof claim 3 wherein the ester comprises from about 20 to about 45 per cent by weight of the totaltcomposition; :1: L mi 5 51A: plasticizedEVinj'zl chlori ares :whiclrcomprises a polymer :ofr'at. least;:about.- 80 per: cent of vinyl chloride and up to;about 20-peri;:cent.;'o1': a copolymerizable monomer, containing intimately dispersed M therein di-2-ethylhexylp,p'-bisphenoxyacet'ate. I

6. The plasticized vinyl chloride resin composition of claim 5 wherein the ester comprises from about 20 'to about 45' per" cent'b'yweightof' the total composition. "L -A plasticiaed vinyl chloride resin which-com- I prises afpolymer of "at least apout ao er 'cent'of vinyl. chloride "and up to about 2Q per cent of a copoly'meriaable monomen' 'c'ontaining" intimately dispersed therein dimethyl-p'b bisphenoxvacetate; 2'5 1 8'."-:'Ihe plasticiz'ed vinyl chloride resin com osi.- tion of claim 7 wherein the ester oomprisesgirom' {about to about 45' per cent'by-weight-lof the ta1 cofn jbsitionji" 15 1 I r I '9.'- A plasticized vinyl chloride resi'riwh c 00111- prises a polymer; of at least-about $0 per cent or vinyl chloride and upto about-2ll -percent'ofi'a copolymeriza'ble monomer, containing'intimately dispersed thereinidiethyl-np bisiiheiibityacetat. 1'0. The plasticized vinyl chloride i esin composition of claim 9 wherein l the ester comprises II 1 2. The 'plasticized vinyl amt-r de resin com; position-f f claim 11 wherein the ester-comprises er ent t'y'weieht of roin about 20 to about-45 per'cent by w 'htof the total-composition. j 13. A plasticized vinyl 'chloride resirnwhich "comprises a polymer of at leastaboutf80 percent of vinyl chloride and'u'p to about 2 0 per cehtof a copolymerizfable; rnonom'eif, containing intimately dispersed therein 'diheXy1 D',p"-b'isphen5 oxvac'etate; I i a t c zed. iy l r -d .re' m? position oi claim 13 whereinfthe'este'r comprises fr'om al'iout20 to a-bout 45' per cent by weight of the'totalcompositiom 1 4 a I i l- O DA REFERENCES CITED- The following references are. of record 'file'o'f" this patent: UNITED STATES PA'rEN 'rsj Number .D'ate chloride r sm which therein di'butyl-p pf-bisphen 

1. A PLASTICIZED VINYL CHLORIDE RESIN WHICH COMPRISES A POLYMER OF AT LEAST ABOUT 80 PER CENT OF VINLY CHLORIDE AND UP TO ABOUT 20 PER CENT OF A COPOLYMERIZABLE MONOMER, CONTAINING INTIMATELY DISPERSED THEREIN AN ESTER OF BISPHENOXYACETIC ACID HAVING THE FORMULA 